Theoretical analysis of the influence of the adsorption process on the voltammetric curves in the case of a second order adsorption step followed by a first order charge transfer reaction: Part III. Variation of the transfer coefficient and application to semiconductor electrodes in l.p.s.v. and s.s.c.v.

Abstract

The kinetic behaviour of a two-step sequential reaction including a 2nd order adsorption process is treated theoretically in the case of semiconductor electrodes. It is shown that the electronic structure of the semiconductor can be taken into account in some simplified cases by introducing a formal transfer coefficient comprised between 0 and 1 and potential independent. In both linear potential sweep voltammetry and steady state cyclic voltammetry, the usual characteristic features ( E M, M, i M) of the voltammetric curves are calculated as a function of the sweep rate for different values of the transfer coefficient.